Cobaltiferous azo-dyestuffs



United States Patent COBALTIFEROUS AZO-DYESTUFFS Arthur Buehler, Rheinfelden, Alfred Fasciati, Bottmingen, and Christian Zickendraht, Binningen, Switzerland, ZSrilngHOIS to Ciba Limited, Basel, Switzerland, a Swiss No Drawing. Application December 15, 1952, Serial No. 326,142

Claims priority, application Switzerland December 15, 1951 14 Claims. (Cl. 260-145) According to this invention valuable new metalliferous azo dyestufis are made by treating with an agent yielding cobalt a mon-oazo-dyestuif free from sulfonic acid and carboxylic acid groups and corresponding to the general formula in which Y represents an amino or hydroxyl group, R1 represents a benzene radical bound to the azo linkage in ortho-position to the hydroxyl group,

1. represents the radical of a coupling component bound to the azo linkage in a position vicinal to the group Y,

and X represents an aryl radical which contains a substituent of the formula compounds obtained by diazotizing an amine of the formula in which the symbols R1 and X have the meanings given in connection with Formula 1 above.

The benzene radical R1 of these amines may contain the amino group in the 2-position, the hydroxyl group in the 1-position and the SOzNH-X group in the 4-, 5- or 6-position. The benzene radical R1 may contain further substituents incapable of salt formation, for

example, a halogen atom or "a nitro group. The aryl radical X may be, for example, a naphthalene or advant-ageously a benzene radical, which contains a sulfonic acid amide group, for example, a sulfonic acid alkylamide or sulfonic acid hydroxyalkylamide group, but advantageously the group of the formula --SOz-NH2, and, if desired, further substituents such as an alkyl group, for example, methyl, a chlorine atom or the like.

Compounds of the Formula 2 may be made, for example, from amines of the formula X-NHz, in which X has the meaning given above, and l-chloro-Z-nltrobenzene-4-sulfonic acid chloride, by reacting the result- 2,788,342 Patented Apr. 9, 1957 ing 1-chloro-2-nitrobenzene-4-sulfonic acid amide with an alkali or alkaline earth metal hydroxide to form the corresponding l-hydroxy-compound, and converting the nitro group in the latter in known manner into an amino group. Instead of 1-chloro-2-nitrobenzene-4-sulfonic acid chloride, there may be used as starting material, for example, 1:Z-benzoxazolone-S-sulfonic acid chloride, in which case after the condensation with the amine of the formula X- NH2 to form the corresponding 1:2-benzoxazolone-S-sulfonic acid amide it is only necessary to hydrolyze the oxazolone ring in order to obtain the compounds of Formula 2.

As amines of the Formula 2 there may be mentioned: 2 amino 1 hydroxybenzene 4 sulfonic acid N lnaphthylamide 4' sulfonic acid amide, 2 amino 1- hydroxy 6 chlorobenzene 4 sulfonic acid phenylamide 3 sulfonic acid amide, 2 amino 1 hydroxy- 6 nitro benzene 4 sulfonic acid phenylamide 4'- sulfonic acid amide, 2 amino 1 hydroxybenzene 4- or 5 sulfonic acid phenylamide 3 sulfonic acid methylamide, 2 amino 1 hydroxybenzene 4 or 5- sulfonic acid phenylamide 3 sulfonic acide p hydroxyethylamide, 2 amino 1 hydroxybenzene 4 or 5 sulfonic acid phenylamide 4' isopropyl or nbu-tylamide, 2 amino 1 hydroxybenzene 4 or 5- sulfonic acid phenylamide 3 sulfonic acid dimethylamide, 2 amino 4 chloro 1 hydroxybenzene 5 or 6 sulfonic acid phenylamide 3' sulfonic acid amide and especially 2 amino 1 hydroxybenzene 4 or 5 sulfonic acid phenylamide 2' 3' or 4' sulfonic acid amide.

As coupling components for preparing the monoazodyestufis serving as starting materials there come into consideration aminoand advantageously hydroxy-compounds, which are free from sulfonic acid and carboxylic acid groups and are capable of coupling in a position vicinal to an amino or hydroxy group. As amino-com pounds of this kind there may be mentioned, for example, naphthylamines such, for example, as p-naphthylamine or l-aminonapththalene-4-su1fonic acid amide. Among the hydroxy-compounds there are also included in addition to aromatic hydroxy-compounds compounds which owe their capacity for coupling to the presence of a keto-methylene group. The latter compounds may contain the keto-methylene group either in an open chain or in a heterocyclic ring.

As hydroxy-compounds of mentioned:

(a) Para-substituted hydroxybenzenes such as 4-methy1-, 3:4-dimethyl-, 4-tertiary-amylor 4-acetylamino-1- hydroxybenzene and 4-methyl-2-acetylamino-l-hydroxybenzene, dihydroxybenzenes such as resorcinol, hydroxynaphthalenes such as 2-hydroxynaphthalene, 2:6-dihydroxynaphthalene, 2-hydroxy-6-bromoor 6-methoxynaphthalene, 1-hydroXy-4-methylnaphthalene, 2hydroxy naphthalene-6-sulfonic acid amide, Lhydroxy-S-chloronaphthalene, l-hydroxy-S:S-dichlorOnaphthalene, and also l-acylamino-7-hydroxynaphthalenes such as l-acetylamino, l-n-butyrylaminoor 1-benzoylamino-7-hydroxynaphthalene, 7-hydroxynaphthyl(l)-carbamic acid ethylor -methyl ester.

(b) Pyrazolones such as 3-methylor 3-phenyl-5- pyrazolone, 1-n-butyl-3-methyl-5pyrazolone, 1-phenyl-3- methyl-S-pyrazolone, l-.(2'-, 3- or 4-chloro)-phenyl- 3-methyl-5-pyrazolone, '5-pyrazolone-3-carboxylic acid amide, S-pyrazolone-B-carboxylic acid-N-rnethyl-, -ethyl-, -isopr0pyl-, -secondary butyl-, -tertiarybutylor -n-butyl amide, 5 -pyrazolone-3-carboxylic acid-N-2-, -3'- or 4- chlorophenylamide, S-pyrazolone-3-carboxylic acid-N- phenylor -p-tolyl-amide, l-phenyl-5-pyrazolone3-carboxylie acid amide, barbituric acids such as barbituric acid itself, dihydroxyquinelines such as 2:4-dihydroxythe above kind there may be water.

' 3 quinoline, acylacetic acid esters or amides such as acetoacetic acid amide, acetoacetic acid N-methyL, -n-butylor -phenyl-amide, acetoacetic acid N-dimethylamide, acetoacetic acid N-2-, -3- or -4-chlorophenylamide, benzoylacetic acid amide or benzoylacetic acid phenylamide.

The amines of the Formula 1 may be diazotized in the usual manner with the use of sodium nitrite and hydrochloric acid. The diazo compounds so obtained may be coupled with the aforesaid coupling components also in the usual manner.

When the coupling reaction has finished the dyestufi' can. easily be separated from the coupling. mixture by filtration, as. they are in general only slightlysoluble: in Indeed in the form of their alkali compounds they are. still. sufliciently solublein. water to enable them to be used: in dyeing from dyebaths which need no addition of acid.

In accordance with. the present. process cobalt com.- pounds. can be obtained, which contain. 1 atom of cobalt for every one or two molecules of monoazo-dyestufi. When ortho:ortho -dihydroxy-monoazo-dyestufis are used as starting materials the cobaltcompounds which contain one atom of.cbalt for every two molecules of monoa-zor dyestuil are especially valuable.

In order to produce such l :2-complexes it is in general desirable to use a quantity of the agent yielding cobalt containing about one gram-atom of cobalt for every two mols of a dyestufi corresponding. to the generalFormuIa l or for about one mol of each of two different dyestulfs in a mixture in which at least one of the dyestuifs corresponds to the general Formula. 1 and/ or to carry out the metallization in a weakly acid. to alkaline medium. As agents yielding cobalt there come into consideration'complex cobalt compounds of aliphatic hydroxy-carboxylic acids or dicarboxylic acids, and simple salts of divalent cobalt such as cobalt sulfate, cobalt acetate or cobalt formate, and, if desired, cobalt hydroxide. The conversion of the dyestuffs into complex cobalt compounds is advantageously carried out at a raised temperature, under atmospheric or superatmospheric pressure, for example,.at the boiling temperature of the reaction mixture, if desired, in the presence of suitable additions, for example, in the presence of salts of organic acids, bases, organic solvents or other agents assisting the formation of complexes.

The metallization described above may be carried out, for example, upon a single dyestutf of the Formula 1. However, it is also possible and in. many cases. of ad-- vantage (for example, to produce various tints), to. metallize a mixture of two different dyestuffs of the Formula 1- or a mixture of a dyestuff. of that formula with: another ortho:ortho.-dihydroxy-monoazo-dycstuif free. from sulfonic acid andwcarboxylic acid groups.

The cobalt compounds so obtained contain one atom of cobalt in complex union with two monoazo-dyestutf molecules, and at least one of the monoazo-dyestuif molecules must correspond to the general Formula 1. Especially valuable are the cobalt compounds of. this kind,

which contain two molecules of the same monoazo-dyestuff of the Formula 1'.

The new cobalt compounds are soluble in water and in weakly acid aqueous media, and are indeed more soluble than the starting materials used for making them. They are suitableifor dyeing various substances such as plastic masses, resins, waxes, lacquers and the like, but more especially for dyeing and printing animal materials such as silk, leather and. especially wool, and also for dyeing and printing synthetic materials composed of superpolyamides or superpolyurethanes. They are suitable above all' for dyeing from a weakly alkaline, neutral or weakly acid, for example, acetic acid, bath. The dyeings so produced are distinguished by their good level character, good properties of. wet .fastness and very good fastness to light.

The following examples illustrate the invention, the parts and. percentages. being by weight unless otherwise stated,.and the relationship of parts by weightto parts by volume being. the same as that of the kilogram. to. the liter:

Example 1 34.3 parts of 2-amino-l-hydroxybenzene-4-sultonic acid anil ide-3'-s-ulfonic acidamide are-dissolved in 200 parts of l N-hydrochloric acid at 40 C. The mixture is cooled to 0 C. by the addition of ice and diazotized at 0-l0 C. with25 parts of a 4 N-solut'ion of sodium nitrite. The resulting yellow diam-suspension is neutralized with sodium carbonate, and then coupled with a solution, cooled to about 5 C., of 14.8 parts of Z-hydroxynaphthalene in 100 parts of water, 4.2 parts of sodium hydroxide and 5 parts of sodium carbonate. When the coupling is finished the precipitated dyestuif is .filtered off, washed with sodium chloride solution of 2 percent, strength and dried. The dyestutt dissolves in dilute sodium carbonate solution with a violet coloration and in concentrated sulfuric acid with a pure blue-red coloration.

4.98 parts of the dyestufif so obtained are suspended in 100 parts of water, then mixed wit-h 8 parts by volume of a 2 N-solution of sodium hydroxide, heated to -C.,.and mixed with 11 parts of a cobalt sulfate-solution having a cobalt content of 2195 percent. After heating fora short time at -90 C. the formation of the complex is complete; The eoba'lticompound of the dyestuff is completely precipitated by neutralization with dilute acetic acid and the addition of sodium chloride. After being filtered oil" and dried, thedyestufl" is a dark brown powder, which dissolves in hot water and dilute sodium carbonate solution with a bordeaux-red coloration and in concentrated sulfuric 'acidwith a pure blue-red coloration, and dyes wool from a neutral or Weakly acid bath bordeaux red tints of very good fastness to washing and light.

In the following table are given-further complex cobalt compounds that can be made in an analogous manner. In column I I-l is given the tint of the dyeing on Wool or fibers of a superpolyamide produced with the cobalt complex of the dyestulf obtained from the components given in eolumns l and II.

I II III Diem-component Coupling component Cobalt com lex OH O Gflwfl Q-GHri l-EN 1 NH:

yellow.

I II III Dino-component Coupling component Cobalt complex O 2 NH; OHr-CO-CHr-i'I-HN D0.

is omHO-e 0mm OH CH:

8.. NH. yellow-brown.

C H:-OO own-Us 0mm OH CH:

4 NH; )N D0.

0 Hr-OO 01 s O NHUS 0m H:

OH I o -NH-CHr-CHz-CHg-CH; 5 NH; I brown-orange.

/N H Hr-OO OzNH S ONH;

6..... NH; blulsh-bordeaux,

own Os 0mm OH NH-O O-GHr-CHz-GH: 7.... QN E: E0 violet-grey.

s om H-OS 011m:

- 8....-.. NH: I brown-orange.

.SOINH BOzNH:

I II III Diazmcomponent Coupling component Cabal; wmplex O H (I) N F O b d H town-re 9 C---N\ O N H S O zNHz 10 --N H, barbiturlc acid yellow-brown.

SO2NH-- S O QNH:

O H 11 @N H; 2 4-d1hydroxyqum01ine orange-brown.

S O :NH:

OH 12 Q-N H1 fl-naphthylamim n grey.

| S 0 :N H

13 -NH 1-acety1am1no-7-hydroxynaphthalene violet-grey.

g 0 :-NH-

S O N H:

14 --NH d0 DQ.

S O zNH: slolNH 0H NH-o o-bcm 15 N H: H 0- Do.

8 O zNH:

I S Oa-NH The Z-amino-1-hydroxybenzene-4-sulfonic acid N- phenylamide-3'-sulfonic acid amide used as diazo component in this example can be made by reacting l-chloro- 2-nitrobenzene-4-sulfonic acid chloride with l-aminobenzene-S-sulfonic acidi amide;

replacing the chlorine atom in the resulting 1-chloro-Z-nitrobenzene-4-sulfonic alcid N-phenylamide-3-sulfonic acidamide by a hydroxyl 75 group by means of an alkalior alkaline earth metal hy- Example 2 4.98 parts of the dyestufi obtained as described in the first paragraph of Example 1 and 5.76 parts of the dyestulf from diazotized Z-amino-1-hydroxybenzene-4-sulfonic acid-2-chloranilide-5'-sulfoni-c acid methylamide and 1- phenyl-3'methyl-5-pyrazolone are suspended in 200 parts of water, then mixed with 16 parts by volume of a 2 N-' solution of sodium hydroxide, and the whole is heated to 80 C. and mixed with 22 parts of a cobalt sulfate solution having a cobalt content of 2.95 percent. After heating the mixture for a short time at 7 882 C. the formation of the complex is complete. The cobalt compound is completely precipitated by the addition of sodium chloride and by neutralization with dilute acetic acid. The filtered off and dried dyestutf is a red-brown powder which dissolves in water With a yellow-red coloration and in concentrated sulfuric acid with a red coloration, and dyes wool from a weakly alkaline, neutral or weakly acid bath red-brown tints.

In the following table are given further cobalt mixed complexes, which are obtained from the monoazo-dyestuffs given in columns I and II. The tints of the dyeings on wool are given in column III.

10 f the boil in the course of V2 hour, and dyeing is continued for hour at the boil. Finally the wool is rinsed with cold water and dried. The wool is dyed aredbrown tint which is fast to washing and has a goodfas'tness to light.

The same dyeing can be produced by dyeing from a neutral bath, that is to say, without the addition of acetic acid to the dyebath. 1

A red-brown dyeing is also produced, by using instead of wool the fibers of a superpolyamide and otherwise proceeding in the same manner.

What is claimed is: t

1. A complex cobalt compound of monoazo-dyestufis free from sulfonic acid and carboxylic acid groups, which contains substantially one atomic proportion of cobalt in complex union for two molecular proportions of monoazodyestufi and in which at least one monoazo-dyestutt present corresponds to the formula wherein Y represents a member selectedfrom the group consisting of a hydroxyl and an amino grou R1 represents a benzene radical bound to the azo linkage in orthoposition relatively to the hydroxyl group, R2Y represents the radical of a coupling component bound to the azo linkage in a position vicinal to the substituent Y, and X represents a benzene radical containing a sulfonic acid amide group.

2. A complex cobalt compound of monoazo-dyestuffs free from sulfonic acid and carboxylic acid groups, which contains one atom of cobalt bound in complex union to I II III

OH HO S OaNH- S OaNH S OzNH OzNHl 4. 98 parts HO N=Ng sonvn,

4. 98 parts O-GHrCHaOH;

OINH,

5. 83 parts reddish bordeaux.

blulsh bordeaux.

Example 3 i substantially two. monoazo-dyestuff molecules both of 2 parts of the cobaltiferous dyestuffs obtained as de- 7. which correspond to the formula scribed in Example 2 are dissolved in Q0 parts of water, 10 parts of crystalline sodium sulfate" are added, and 100 parts of well wettedawool are entered at-40 5.0": G; into the dyebath so preparedfi Thereare: then added ,2 parts of acetic acid of 40 percent. strength, the bath is raised to 7 6; wherein Y represents a member selected from the group- 'wliferein k s represent's a1benzene:radieal, n represents a whole number up to two;-R1 represents a'ben'ze'ne radical bound to the azo linkagein ortho-ppsition relatively to the hydroxyl group and Rz;OH represents the radical of a coupling component bound to-th'e'lazo linkage in a position vicinal to the HO-group.

4. A complex cobalt compound of monoazo-dyestulis ftee-fromgsulfonic acjd' 'a'ndcarboxylic :acidgrou'ps;v which icontains one -.a tom=of cobalt boundin' complex union with substantially two-monoazo'-dyestult molecules one of which corresponds I to the formula SOsNH: and the other to the formula SOs-NH wherein R represents a member selected from the group consisting of a Z-hydroxynaphthalene radical bound to the azo group in l-position and a -pyrazolone radical bound to the azo linkage in 4-position, X represents amember of the group consisting of a chlorine and-abydrogen atom and n is a whole number up to 2.

5. A complex cobalt compound of monoazo-dyestuit's free from sulfonic acid and carboxylic acid groups, which contains one atom of cobalt bound in complex union to substantially two monoazo-dyestufi molecules] both of which correspond to the formula herein Karwrments: a b nzene radical.

6. icomplpxucpbalt icomppund of monoazmdyestuifs free from sulfonic acid and carboxylic zacidzgroups; which contains..oneiatom-1of cobalt: bound in complex union to substantially .two monoazo dyestulf -molecules both of 5 wh-ichcorrespond to sthe' formula' whe ein-r1"?: biiesent fi razl ad c bou t th 'f olinkaa AQQSitiQ -Q ial bmneund t mQma oy mfi d. dia l s a dj ps which coba t: ounill flPlfi u o to noazo-dyestufl? molecules both of 9 11 man two m btr s b dittov th tfom soma- 1 92 131, wherein P2 represents a. 1-aryl-3-methyl-5-pyrazo1one radical bound to the azo linkage in -4-position.

8. A complex cobalt compound of monoazo-dyestuffs free from sulfonic'acidand carb'oxylic acid groups, which contains one atom of cobalt bound in complex union to "substantially "twp monoazo dyestuffmolecules 'both of which correspend to the formula wherein R; represents a 2 hydroxynaphthalene radical bound to the azo linkage in l-position.

9, A complex cobalt compound :of 'monoazo-dyestulfs free from sulfonic acidandcarboxylicacid groups, which Contains vone .atom of cobalt bound incomplex union to substantially two monoazo-dyestufl molecules both of which correspond to the formula on no N=N- I HN Sbr-NH loo-411M wherein-1i is a whole 'nu mber up to 5. v 10.} Thc eomp1ex;cobaltcompound-which contains one 15' atom of cobalt-boundin complex union to substantially two monoazo-dyestuft molecules both of which corretwo monoazo-dyestuff molecules both of which correspond to the formula spond to the formula S m-NEG A OnNH:

11. The complex cobalt compound which contains one atom of cobalt bound in complex union to substantially two monoazo-dyestuff molecules both of which correspond to the formula on H0 HO 1 on A N=N N=N--C/ I $11. SOB-NHQ H Orr-N ONH.

and the other to the formula 12. The complex cobalt compound which contains one atom of cobalt bound in complex union to substantially two monoazo-dyestufi' molecules both of which corre- SOflNH spond to the formula OH HO SOgNH-CH; N=N References Cited in the file of this patent EN UNITED STATES PATENTS 2,443,226 Carson June 15, 1948 02-NH CO(CH|):CHt 2,495,244 Felix et a1. Jan. 24, 1950 2,565,898 Widmer Aug. 28, 1951 2,572,394 Ruckstuhl et al. Oct. 23, 1951 2,597,676 Schetty May 20, 1952 SOINHI 2,606,185 Widmer Aug. 5, 1952 2,634,263 Steinemann Apr. 7, 1953 OTHER REFERENCES 13. The complex cobalt compound WhlCh contains one Crossley Metalhzed Azo Dyes, American Dyestufi Rep., atom of cobalt bound in complex union to substantially Mar. 7, 1938, pgs. 124-5. 

1. A COMPLEX COBALT COMPOUND OF MONOAZO-DYESTUFFS FREE FROM SULFONIC ACID AND CARBOXYLIC ACID GROUPS, WHICH CONTAINS SUBSTANTIALLY ONE ATOMIC PROPORTIONS OF COBALT IN COMPLEX UNION FOR TWO MOLECULAR PROPORTIONS OF MONOAZODYESTUFF AND IN WHICH AT LEAST ONE MONOAZO-DYESTUFF PRESENT CORRESPONDS TO THE FORMULA 